Catalytic Reduction of Dinitrogen to Ammonia and Hydrazine Using Iron- Dinitrogen Complexes Bearing Anionic Benzene-Based PCP-Type Pincer Ligands

被引：12

作者：

Kuriyama, Shogo

Kato, Takeru

Tanaka, Hiromasa ^{[1
]}

Konomi, Asuka ^{[2
]}

Yoshizawa, Kazunari ^{[2
]}

Nishibayashi, Yoshiaki

机构：

[1] Daido Univ, Sch Liberal Arts & Sci, Minami Ku, Nagoya, Aichi 4578530, Japan

[2] Kyushu Univ, Inst Mat Chem & Engn, Nishi Ku, Fukuoka, Fukuoka 8190395, Japan

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 2022年 / 95卷 / 04期

关键词：

Nitrogen fixation; Iron; Ammonia; MOLECULAR-ORBITAL METHODS; AB-INITIO PSEUDOPOTENTIALS; GAUSSIAN-TYPE BASIS; N-2-TO-NH3; CONVERSION; N-2; REDUCTION; BASIS-SETS; C-H; NITROGENASE; CARBON; COFACTOR;

D O I：

10.1246/bcsj.20220048

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Among synthetic models of nitrogenases, iron-dinitrogen complexes with an Fe-C bond have attracted increasing attention in recent years. Here we report the synthesis of square-planar iron(I)-dinitrogen complexes supported by anionic benzene-based PCP- and POCOP-type pincer ligands as carbon donors. These complexes catalyze the formation of ammonia and hydrazine from the reaction of dinitrogen (1 atm) with a reductant and a proton source at -78 degrees C, producing up to 252 equiv of ammonia and 68 equiv of hydrazine (388 equiv of fixed N atom) based on the iron atom of the catalyst. Anionic iron(0)-dinitrogen complexes, considered an essential reactive species in the catalytic reaction, are newly isolated from the reduction of the corresponding iron(I)-dinitrogen complexes. This study examines their reactivity using experiments and DFT calculations.

引用

页码：683 / 692

页数：10